Process of retarding the setting of casein glue and dry glue base for use in such processes



Patented Oct. 27, 1931 UNITED STATES PATENT OFFICE LAWRENCE BRADSHAW ANDHENRY V. DUNEAM, OF BAINBRIDGE, NEW YORK, AS-

SIGNORS, BY MESNE ASSIGNMENTS, TO THE CASEIN'MANUFACTURING COMPANY OFAMERICA, IN C., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE PROCESS OFRETARDING THE SETTING OF CASEIN GLUE AND DRY GLUE BASE FOR I USE IN SUCHPROCESSES No Drawing. Application filed April 2,

This invention has for its object improvements in casein waterproofglues or cements and in a novel glue base. which when prop erlyincorporated with water will produce such an adhesive. It is well knownthat glues prepared from different commercial caseins exhibit widevariations in consistency when mixed with a given proportion of waterand also difler greatly in their subsequent behavior, notably in theinterval oftime which may elapse between-the initial mixing with waterand the point at which the glue sets, i. e., becomes too thick tospread. Various methods have been proposed to control this interval,generally termed the life of the glue, such as the addition of animalglue or salts of the alkali or alkaline earth metals. The use of animalglue for this purpose is uneconomical, since its natural strength, whichotherwise would contribute to the adhesiveness of the mixture,depreciates considerably under these conditions. The addition to caseinglues of alkali metal phosphates, fluorides and other salts which byinteraction with lime liberate caustic alkalies is undesirable beyond acertain point; that is to say,

peanut meal added to casein waterproof glues have a marked effect inretarding the setting of the liquid glues, thereby extending the life ofsuch glues. As an example, the rates of change in the viscosity of acommercial casein glue (A) and of the same glue with 7% (B) and with 15%(C) respectively of pulverized cottonseed meal added are comared below.One part of each of the glue Eases was mixed with two parts of water atF., producing a slight rise in temperature. The viscosities weredetermined at 70 F., in all cases. The values represent readings on theStormer viscosimeter (provided with a 500 gram weight) at regularintervals after 1926. Serial No. 99,423.

mixing. the conditions of making and testing the tlbhree liquid glues A,B and C, being identlca 1 hr. 3 hrs. 5 hrs. 7 hrs. 9 hrs 11 hrs 13 hrs.

A 26 9 2 set B 33 18 I 10 5 1 not set C 27 21 15 8 5 3 1% 1 hr. 3 hrs. 5hrs. 7 hrs. 8 hrs.

A' 25 10 6 set P 24 20 9 2 not set;

We find that by substituting 50% of the casein in a regular third goodcommercial casein glue (A") by an equivalent amount of the pulverizedpeanut meal a glue (Q) is obtained which undergoes practically no changein viscosity over a long period, as shown in the comparison below:

1 hr. 3 hrs. 5 hrs. 7 hrs. 8 hrs.

A 20 8 23 36 set Q 20 20 21 22 25 The commercial casein glue referred toabove, was in each case, a pulverulent mixture consisting of casein,hydrated lime and alkali-metal salts capable of reacting with thehydrated lime (when water is added) to produce caustic alkali andinsoluble calcium salts. The proportions of said components were similarto the proportions given in the present application.

It will also be understood that by varying the proportions of theprotein-rich meal added, the life of the glue can be controlled withinwide limits. We prefer to use meal which has been ground to pass througha 120 mesh screen, although a coarser product of approximately 80 meshhas given good results in casein waterproof glues. With the finer meal asmoother glue is obtained.

In carrying out the inventionthe casein pressing cottonseed (a (that is,casein from milk) is mixed dry, with an appropriate amount of thevegetable meal, and to this mixture is added an alkaline earth metalhydroxide and preferably also one or more alkali metal salts capable ofdissolving the proteins. The following examples of mixtures which havegiven satisfactory results-when applied to joints and laminated woodswill serve to illustrate more particularly the character of theinvention, but we do not desire to be limited to the particularcompounds or proportions herein set forth. (The parts are b weight).

7 Example 1. asein 60 'parts; cottonseed meal 120 mesh, 10 parts;hydrated lime parts; sodium fluoride 5 parts, sodium carbonate 5 parts)tri-sodium phosphate 3 parts,

(98 parts in al Emmple 2.-Oasein 33 parts, cottonseed meal 33 parts,hydrated lime parts, sodium fluoride 6 parts sodium carbonate 8 parts,(100 parts 111 all).

Example 3.-Casein 50 parts, cottonseed meal 20 parts, hydrated lime 15parts, magnesium oxide 5 parts, sodium fluoride 7 parts,

.til'i-sodium phosphate 3 parts, (100 parts in a sample 4.Casein 40parts, peanut meal 30 parts, hydrated lime 18 parts, sodium fluoride 5parts, sodium carbonate 5 parts, sodium arsenate 1 art, (99 parts inall). 4

Ewamle 5. asein parts, peanut meal 22 parts, hydrated lime 18 parts,sodium carbonate 10 parts, (100 parts in all).

Ewample 6-.-Casein 54 parts, peanut meal 30 parts, hydrate'd'lime 16parts. Onepart of the dry mixture is to be incorporated with I about 3parts of cold water.

These examples indicate the dry materials which are mixed together toform' the glue base. The dry mixture is incorporated with water (at orjust before the time of use), by the methods well known to users ofcasein glues. We prefer to use from 2 to 2 parts of cold water to 1 partof the dry water is put into a kettle rovided with an eflicient stirringdevice; t e dry glue base (e. one of the above formulas) is added slow yminutes and the glue is then ready for use. The term casein is usedherein in its usual significance, to denote certain coagulablephosphorus-containing roteid matter as found in milk and skim milk.

The cottonseedmeal preferably used (as re-- ferred to in Examples 1, 2and 3) is the product obtained by grindin the cake left after r removalof the ma or (part of the hulls, and adhering fine lint if esired theoil ;-itusually-still contains some oil (perhaps -78%). It will beunderstood that the further removal ofoil by solvent treatment of thepress cake, or the direct extraction of the oil from the seed withsuitable solvents base. The l and mixed thoroughly for about 20' for thepurpose of expressing.

used in aprecisely similar manner, and is accordingly considered as anequivalent, and the term protein-rich seed meal as used in the claims isintended to cover cotton seed meal and peanut meal. a

The term alkaline earth oxide as used in the appended claims is intendedto embrace this material in the anhydrous or hydrated states, and alsothe corresponding oxide and hydroxide of magnesium. The term salt isintended to be used in the generic sense to include the singular orplural forms, i. e. one salt or several salts. The statement in anyclaim that the material will pass a screen of particular mesh does notmean that'the material (or some part thereof) will not pass through afiner screen. Alkaline substances, e. g. sodium carbonate, borax, etc.are capable (with Water) of dissolving casein and meal proteids.

We claim 1. A new dry base for use in making an adhesive materlalcomprising casein as a substantial ingredient together with asubstantial amount of a protein-rich seed meal, incorporated with analkaline earth oxide and a Water-soluble alkali metal salt which reactsalkaline to litmus, and which salt is capable of reacting in thepresence of water, with such alkaline earth oxide, which base is adaptedupon being subsequently mixed with suflicient water, to produce a fluidadhesive of spreadable cons1stency. I 2. A new dry base for use inmaking an adhesive composition containing casein as a major ingredienttogether-with a relatively smaller but substantial amount of cotton seedmeal from which most of the oil has been mixed with sufiicient water toreduce a fluid" adhesive of spreadable consis ncy.

3. A new dry base for the manufacture of glue and adhesive compositions,such base comprisinfg casein, a lesser but substantial amount 0protein-rich seed meal ground to pass an 80 to meshscreen, an alkalineearth oxide in amount suificient to maintain the mixture alkaline, and asubstantial amount of a water-soluble alkali metal salt which in aqueoussolution will react with the said alkaline earth oxide to-produce asolvent forthe caseinand for the protein of said protein-rich seed meal,which base, upon being subsequently mixed with cold water will form afluid adhesive.

4. A new dry base for the manufacture of glue and adhesive compositions,such base comprising casein and a protein-rich seed meal from which alarge part of the hull substance has been removed, ground to pass an 80to 120 mesh screen, such casein and seed meal both being present insubstantial amount, an alkaline earth oxide, in amount sufficient tomaintain the mixture alkaline and comprising casein, a lesser butsubstantial amount of protein-rich seed meal from which a substantialpart at least of the oil has been removed, ground to pass an 80 to 120mesh screen, an alkaline earth oxide in amount suflicient to maintainthe mixture alkaline, and a substantial amount of a water-soluble alkalimetal salt which in aqueous solution will react with the said alkalineearth oxide to produce a solvent for the protein, which base, upon beingsubsequently mixed with cold water will form a fluid adhesive.

6. Av new dry base'for the manufacture of glues and adhesivecompositions, such base comprising casein and a protein-rich seed mealfrom which a substantial part at least of the oil has been removed, themajor part at least of which meal is fine enough to pass an 80 to 100mesh screen, and an alkaline earth oxide in amount sufficient tomaintain the oxide in amount suflicient to maintain the mixture alkalinewhen water is added, the amount of such meal being sufiicient tosubstantially lengthen the life of the adhesive prepared from said base,as compared with a casein glue without such seed meal.

I 8. A new dry base for use in making an adhesive material comprisingcasein as a sub stantial ingredient, together with a substantial amountof a protein-rich seed meal, incorporated with an alkaline earth oxideand a water-soluble alkali .metal salt, which salt is capable ofreacting, in the presence of water, with such alkaline earth oxide,which base, upon being subsequently mixed with suflicient water, willproduce an adhesive of fluid spreadable consistency.

9. A novel material in the glue art, the same being an intimate drymixturecomprising casein and a protein-rich seed meal, the former beingin excess of the latter.

10. A novel material in the glue art, the same being an intimate drymixture comprising casein and a protein-rich seed meal, the amount ofcasein being substantially greater than the amount of protein containedin the seed meal. I

11. A dry glue base containing about equal parts of casein and of a dryprotein-rich seed meal, together with smaller amounts of an alkalineearth metal oxide and of alkaline-reacting sodium salt, the latter beingin amount suflicient, by reaction with the said alkaline earth metaloxide, to form a solvent for the casein and meal proteids present.

12. A process for producing a glue of comparatively long working lifefrom a glue base including casein, a water-soluble alkali metal saltwhich is alkaline to litmus, and an alkaline earth metal oxide, whichprocess comprises incorporating a protein-rich seed meal in such gluebase, and thereafter mixing this new glue base with water, theproportion of the protein-rich seed meal used being sufiicient to retardthe setting of the glue produced by said admixture with water.

In testimony whereof we allix our signatures.

LAWRENCE BRADSHAW. HENRY V. DUNHAM.

